EP1230200B1 - C13-alkoholgemisch und funktionalisiertes c13-alkoholgemisch - Google Patents

C13-alkoholgemisch und funktionalisiertes c13-alkoholgemisch Download PDF

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EP1230200B1
EP1230200B1 EP00987265A EP00987265A EP1230200B1 EP 1230200 B1 EP1230200 B1 EP 1230200B1 EP 00987265 A EP00987265 A EP 00987265A EP 00987265 A EP00987265 A EP 00987265A EP 1230200 B1 EP1230200 B1 EP 1230200B1
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Prior art keywords
catalyst
weight
alcohol mixture
butene
reaction
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English (en)
French (fr)
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EP1230200A2 (de
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Edgar Zeller
Marc Walter
Wolfgang Richter
Klaus Diehl
Michael Röper
Jürgen Tropsch
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • C11D7/262—Alcohols; Phenols fatty or with at least 8 carbon atoms in the alkyl or alkenyl chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/10—Saturated ethers of polyhydroxy compounds
    • C07C43/11—Polyethers containing —O—(C—C—O—)n units with ≤ 2 n≤ 10
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols

Definitions

  • the present invention relates to a C 13 alcohol mixture which is particularly suitable for the preparation of surfactants. It also relates to a functionalized C 13 alcohol mixture with surfactant properties.
  • fatty alcohols with about 8 to 20 carbon atoms use for the production of nonionic and anionic surfactants.
  • the alkoxylates obtained can either be used directly as non-ionic surface-active substances used or by a further functionalization, e.g. B. by sulfation or Phosphating, converted into anionic surface-active substances become.
  • the application properties of these surfactants, z. B. their wetting capacity, foaming, fat dissolving capacity, biodegradability, etc. are essentially due to the Chain length and the degree of branching of the hydrophobic hydrocarbon residue of the alcohol used.
  • Alcohols that are well suited for further processing into effective surfactants are also known as surfactant alcohols.
  • Fatty alcohols are from both native and synthetic sources Way, e.g. B. by building from educts with a lower Number of carbon atoms available. So you get z. B. after the SHOP process (Shell Higher Olefine Process) starting from Ethene olefin fractions with one for further processing Suitable number of carbon surfactants.
  • SHOP process Shell Higher Olefine Process
  • the functionalization of the Olefins to the corresponding alcohols are carried out, for. B. by Hydroformylation and hydrogenation.
  • a disadvantage of the ethylene based processes for the production of fatty alcohols are the high cost of the raw material, making this process economical are disadvantaged.
  • Olefins with a carbon number suitable for further processing to surfactant alcohols can also be obtained by oligomerization of C 3 -C 6 -alkenes, such as in particular propene or butene or mixtures thereof.
  • halogen content causes accelerated corrosion the parts of the system that come into contact with the product flow.
  • traces of halogen in the higher olefins affect the activity of the catalysts in the further processing stages, especially the hydroformylation and hydrogenation catalyst.
  • the Halogen traces are predominantly in the form of halogen-organic compounds in front. The presence of such connections in products, which are processed into consumer products is over basic considerations undesirable.
  • WO 98/23566 describes a mixture of branched primary alcohols which can be obtained, inter alia, by dimerizing a C 6 -C 10 olefin in the presence of a homogeneous dimerization catalyst and then converting the branched C 12 -C 20 olefin obtained to the mixture of branched primary alcohols ,
  • the object of the present invention is halogen-free Surfactant alcohols and surfactants obtained from them are available to deliver.
  • the branching structure of the surfactant alcohols is said to be be a balanced range of properties regarding surface active properties, ecotoxicity and biological Degradability of the surfactants is given.
  • the invention also relates to a C 13 alcohol mixture which can be obtained by the above process.
  • the C 13 alcohol mixture according to the invention is preferably essentially halogen-free, ie it contains less than 3 ppm by weight, in particular less than 1 ppm by weight, halogen, in particular chlorine.
  • C 12 olefins are built up from C 4 bodies in a first step.
  • butenes are oligomerized in a manner known per se on a nickel-containing heterogeneous catalyst.
  • the butene trimers, ie C 12 olefins are further processed for the present purposes.
  • the butenes used must be predominantly linear, ie the isobutene content should be less than 5% by weight.
  • the butenes can contain an admixture of saturated C 4 hydrocarbons, which act as diluents in the oligomerization.
  • the heterogeneous, nickel-containing catalysts that can be used can have different structures, with nickel oxide-containing catalysts being preferred.
  • Catalysts known per se can be used, as described in CT O'Connor et al., Catalysis Today, Vol. 6 (1990), pp. 336-338.
  • supported nickel catalysts are used.
  • the carrier materials can e.g. As silica, alumina, aluminosilicates, aluminosilicates with layer structures and zeolites such as mordenite, faujasite, zeolite X, zeolite-Y and ZSM-5, zirconium oxide, which is treated with acids, or sulfated titanium dioxide.
  • Precipitation catalysts are particularly suitable, which by mixing aqueous solutions of nickel salts and silicates, for. B. sodium silicate with nickel nitrate, and optionally aluminum salts such as aluminum nitrate, and calcining are available. Furthermore, catalysts can be used which are obtained by incorporating Ni 2+ ions by ion exchange into natural or synthetic layered silicates, such as montmorillonites. Suitable catalysts can also be obtained by impregnating silica, alumina or aluminosilicate with aqueous solutions of soluble nickel salts, such as nickel nitrate, nickel sulfate or nickel chloride, and then calcining.
  • nickel salts and silicates for. B. sodium silicate with nickel nitrate, and optionally aluminum salts such as aluminum nitrate, and calcining are available.
  • catalysts can be used which are obtained by incorporating Ni 2+ ions by ion exchange into natural or synthetic layered silicates, such as montmorillonites
  • Catalysts which essentially consist of NiO, SiO 2 , TiO 2 and / or ZrO 2 and optionally Al 2 O 3 are particularly preferred. Most preferred is a catalyst which contains 10 to 70% by weight of nickel oxide, 5 to 30% by weight of titanium dioxide and / or zirconium dioxide, 0 to 20% by weight of aluminum oxide as the active ingredients and the remainder being silicon dioxide.
  • a catalyst can be obtained by precipitation of the catalyst mass at pH 5 to 9 by adding an aqueous solution containing nickel nitrate to an alkali water glass solution which contains titanium dioxide and / or zirconium dioxide, filtering, drying and tempering at 350 to 650 ° C.
  • DE-4339713 for the preparation of these catalysts, reference is made in detail to DE-4339713. Reference is made in full to the disclosure of this publication and the prior art cited therein.
  • the catalyst is preferably in lumpy form, e.g. B. in Form of tablets, e.g. B. with a diameter of 2 to 6 mm and a height of 3 to 5 mm, rings with z. B. 5 to 7 mm outer diameter, 2 to 5 mm high and 2 to 3 mm hole diameter, or Strands of different lengths of a diameter of e.g. B. 1.5 up to 5 mm.
  • Such shapes are made in a manner known per se by tableting or extrusion, usually using a Tableting aids, such as graphite or stearic acid, obtained.
  • the C 4 hydrocarbon stream generally contains 50 to 100% by weight, preferably 60 to 90% by weight, butenes and 0 to 50% by weight, preferably 10 to 40% by weight, butanes.
  • the butene fraction comprises less than 5% by weight, in particular less than 3% by weight, of isobutene, based on the butene fraction.
  • the butene fraction generally has the following composition (in each case based on the butene fraction): 1-butene 1 to 50% by weight cis-2-butene 1 to 50% by weight trans-2-butene 1 to 99% by weight isobutene 1 to 5% by weight
  • raffinate II is used as a particularly preferred feedstock, which is an isobutene-depleted C 4 cut from an FCC system or a steam cracker.
  • diolefins or alkynes are present in the C 4 hydrocarbon stream, they are preferably removed from the same to less than 10 ppm by weight, in particular less than 5 ppm by weight, particularly preferably less than 1 ppm by weight, before the oligomerization. They are preferred by selective hydrogenation, e.g. B. removed according to EP-81041 and DE-1568542.
  • oxygen-containing compounds such as alcohols, aldehydes, ketones or ethers
  • the C 4 hydrocarbon stream can be advantageously via an adsorbent, such as. B. a molecular sieve, in particular one with a pore diameter of> 4 ⁇ to 5 ⁇ , are passed.
  • the concentration of oxygen-containing compounds in the C 4 hydrocarbon stream is preferably less than 1 ppm by weight, in particular less than 0.5 ppm by weight.
  • the contacting with the oligomerization catalyst takes place preferably at temperatures from 30 to 280 ° C, in particular 30 to 140 ° C and particularly preferably from 40 to 130 ° C. It is preferably carried out at a pressure of 10 to 300 bar, in particular from 15 to 100 bar and particularly preferably from 20 to 80 bar. The pressure is expediently set so that the C 4 hydrocarbon stream is liquid or in the supercritical state at the selected temperature.
  • the C 4 hydrocarbon stream is usually passed over one or more fixed catalyst beds.
  • Suitable, if appropriate, pressure-resistant reaction apparatuses for bringing the hydrocarbon stream into contact with the heterogeneous catalyst are known to the person skilled in the art. These include the generally customary reactors for gas / solid reactions or liquid / solid reactions. Are suitable for. B. shell and tube reactors or shaft furnaces.
  • the oligomerization can be done in a single reactor be carried out, wherein the oligomerization catalyst in a single or more fixed beds arranged in the reactor can be.
  • one reactor cascade can consist of several, preferably two reactors connected in series be, with the passing of the or the last reactor the Cascade upstream reactor or reactors the oligomerization the butene is only operated up to a partial turnover and the desired final conversion only when passing the reaction mixture is achieved by the last reactor in the cascade.
  • Individual reactors in the reactor cascade can use the oligomerization catalyst in a single or in several catalyst beds be arranged.
  • the preferred reactor is usually a vertical one loaded with the catalyst cylindrical tube made of the olefin-rich hydrocarbon mixture z. B. from top to bottom.
  • the oligomers formed are cascade from the reactor discharge separated from the unreacted butenes and butanes.
  • the educated Oligomers can be processed in a subsequent vacuum fractionation step to be separated or purified.
  • oligomers formed exempted reactor discharge which essentially consists of unconverted Butenes and butanes exist, in whole or in part due.
  • a C 12 olefin fraction is isolated from the reaction discharge from the oligomerization reaction in one or more separation steps.
  • Suitable separation devices are the usual apparatuses known to the person skilled in the art. These include e.g. B. distillation columns, such as plate columns, which can be equipped if desired with bells, sieve plates, sieve plates, valves, side vents etc., evaporators, such as thin-film evaporators, falling film evaporators, wiper blade evaporators, Sambay evaporators etc. and combinations thereof.
  • the C 12 olefin fraction is preferably isolated by fractional distillation.
  • the ISO index of the C 12 olefin fraction which indicates the average number of branches, is usually 1.9 to 2.3, preferably 2.0 to 2.3.
  • the ISO index can e.g. B. can be determined by hydrogenating a sample of the C 12 olefin fraction to the dodecanes and determining the mean number of methyl groups in the 1 H-NMR spectrum on the basis of the signal area to be assigned to the methyl groups and the signal area to be assigned to the total protons.
  • the ISO index is the average number of methyl groups minus two.
  • the isolated C 12 olefin fraction is hydroformylated to C 13 aldehydes, and then hydrogenated to alcohols 13 C.
  • the alcohol mixtures can be prepared in one step or in two separate reaction steps.
  • the amount of the hydroformylation catalyst is generally 0.001 to 0.5% by weight, calculated as cobalt metal, based on the amount of olefins to be hydroformylated.
  • the reaction temperature is generally in the range of about 100 to 250 ° C, preferably 150 to 210 ° C.
  • the reaction can an increased pressure of about 10 to 650 bar. It is preferred that the hydroformylation be carried out in the presence of Water takes place; however, it can also be used in the absence of water be performed.
  • Carbon monoxide and hydrogen are usually in the form of a Mixture, the so-called synthesis gas, used.
  • the composition of the synthesis gas used can vary within a wide range.
  • the molar ratio of carbon monoxide to hydrogen is usually about 2.5: 1 to 1: 2.5.
  • a preferred ratio is about 1: 1.5.
  • the hydroformylation-active cobalt catalyst is HCo (CO) 4 .
  • the catalyst can be outside the hydroformylation reactor, e.g. B. from a cobalt (II) salt in the presence of synthesis gas, preformed and introduced together with the C 12 olefins and the synthesis gas into the hydroformylation reactor.
  • a cobalt (II) salt in the presence of synthesis gas, preformed and introduced together with the C 12 olefins and the synthesis gas into the hydroformylation reactor.
  • the formation of the catalytically active species from catalyst precursors can only take place under the hydroformylation conditions, i.e. h in the reaction zone.
  • Suitable catalyst precursors are cobalt (II) salts, such as cobalt (II) carboxylates, e.g. B. cobalt (II) formate or cobalt (II) acetate; and cobalt (II) acetylacetonate or
  • the cobalt catalyst homogeneously dissolved in the reaction medium can be from Hydroformylation product are suitably separated by the reaction discharge of the hydroformylation in the presence of a acidic aqueous solution is treated with oxygen or air.
  • the cobalt catalyst forms cobalt (II) salts oxidatively destroyed.
  • the cobalt (II) salts are water-soluble and are extracted into the aqueous phase, which is separated and recycled to the hydroformylation process can.
  • the aqueous cobalt (II) salt solution is then returned to the process.
  • suitable cobalt (II) salts come mainly cobalt (II) acetate and cobalt (II) formate into consideration.
  • the formation of the Cobalt catalyst, the extraction of the cobalt catalyst in the organic phase and the hydroformylation of the olefins in one Step done by adding the aqueous cobalt (II) salt solution to the Olefins and optionally the organic solvent as well Hydrogen and carbon monoxide in the reaction zone under hydroformylation conditions, z. B. by means of a mixing nozzle, intimately in Be brought in contact.
  • the crude aldehydes or aldehyde / alcohol mixtures obtained in the hydroformylation can if desired before the hydrogenation isolated and, if appropriate, by customary processes known to the person skilled in the art getting cleaned.
  • Suitable hydrogenation catalysts are generally transition metals, such as B. Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru etc. or their mixtures, which increase activity and stability on supports such as B. activated carbon, aluminum oxide, diatomaceous earth, etc. can be applied.
  • B. activated carbon, aluminum oxide, diatomaceous earth, etc. can be applied.
  • Fe, Co and preferably Ni also in the form of Raney catalysts used as a metal sponge with a very large surface become.
  • a Co / Mo catalyst is used for surfactant alcohols.
  • the hydrogenation the oxo aldehydes depend on the activity of the catalyst preferably at elevated temperatures and increased pressure.
  • the hydrogenation temperature is preferably about 80 to 250 ° C, preferably the pressure is about 50 to 350 bar.
  • the C 13 alcohol mixture according to the invention can be obtained in pure form from the reaction mixture obtained after the hydrogenation by customary purification processes known to those skilled in the art, in particular by fractional distillation.
  • the C 13 alcohol mixture according to the invention preferably has an average degree of branching of 2.1 to 2.5, in particular 2.2 to 2.4.
  • the number of methyl groups in one molecule of the alcohol minus 1 is defined as the degree of branching.
  • the mean degree of branching is the statistical mean of the degree of branching of the molecules of a sample.
  • the average number of methyl groups in the molecules of a sample can easily be determined by 1 H-NMR spectroscopy. For this purpose, the signal area corresponding to the methyl protons in the 1 H-NMR spectrum of a sample is divided by three and related to the signal area of the methylene protons in the CH 2 -OH group divided by two.
  • the alcohol mixtures are alkoxylated by reaction with at least one alkylene oxide.
  • the alkylene oxides are preferably selected from compounds of the general formula I. wherein R 1 represents hydrogen or a straight-chain or branched C 1 to C 16 alkyl radical, and mixtures thereof.
  • the radical R 1 in the formula I is preferably a straight-chain or branched C 1 to C 8 alkyl radical, in particular a C 1 to C 4 alkyl radical.
  • the alkylene oxides are preferably selected from ethylene oxide, Propylene oxide, butylene oxide and mixtures thereof.
  • the alcohol mixtures are reacted with the alkylene oxide (s) by customary methods known to those skilled in the art and in therefor usual equipment.
  • Alcohol mixtures can by the molar ratio of Alcohol can be determined to alkylene oxide.
  • Alkoxylation is preferred Alcohol mixtures with about 1 to 200, preferably about 1 to 50, in particular 1 to 10 alkylene oxide units.
  • the alcohol mixtures can only be mixed with an alkylene oxide or reacted with two or more different alkylene oxides become.
  • the alcohol mixtures with a Mixtures of two or more alkylene oxides contain the resulting ones Alkoxylates essentially the alkylene oxide units statistically distributed.
  • the alkylene oxides are separated one after the other used, result in alkoxylates which correspond to the Order of addition of the alkylene oxide units in the form of blocks polymerized included.
  • the alkoxylation can be catalyzed by strong bases, such as alkali metal hydroxides and alkaline earth metal hydroxides, Bronsted acids or Lewis acids, such as AlCl 3 , BF 3 etc.
  • strong bases such as alkali metal hydroxides and alkaline earth metal hydroxides, Bronsted acids or Lewis acids, such as AlCl 3 , BF 3 etc.
  • the alkoxylation is preferably carried out at temperatures in the range from about 80 to 250 ° C, preferably about 100 to 220 ° C.
  • the Pressure is preferably between ambient pressure and 600 bar.
  • the alkylene oxide can be admixed with an inert gas, z. B. from about 5 to 60%.
  • the functionalized alcohol mixtures obtained by alkoxylation show a very good surface activity and can be used as nonionic surfactants in a variety of applications be used advantageously, e.g. B. as a surfactant, dispersant, Paper auxiliaries, dirt solvents, corrosion inhibitors, Aid for dispersions or incrustation inhibitor.
  • the alcohol mixtures are glycosidated by one, two or more reactions of the alcohol mixtures according to the invention with mono-, di- or polysaccharides.
  • the reaction is carried out using customary methods known to the person skilled in the art. On the one hand, this includes acid-catalyzed conversion with dehydration. Suitable acids are e.g. B. mineral acids such as HCl and H 2 SO 4 .
  • oligosaccharides with statistical chain length distribution are obtained.
  • the average degree of oligomerization is preferably 1 to 3 saccharide residues.
  • the saccharide can first be reacted with a low molecular weight C 1 - to C 8 -alkanol, such as.
  • acetalized As ethanol, propanol or butanol, acetalized.
  • the acetalization is preferably acid-catalyzed.
  • the resulting glycoside with the low molecular weight alcohol can then be reacted with an alcohol mixture according to the invention to give the corresponding glycosides.
  • Aqueous saccharide solutions are generally also suitable for this reaction.
  • the saccharide can first be converted into the corresponding O-acetylhalosaccharide by reaction with a hydrogen halide and then glycosidated with an alcohol mixture according to the invention in the presence of acid-binding compounds.
  • Monosaccharides are preferably used for glycosidation.
  • hexoses such as glucose, fructose, galactose, Mannose etc. and pentoses such as arabinose, xylose, ribose etc. used.
  • Glucose is particularly preferably used.
  • the Saccharides can be used individually or in the form of mixtures become. Glycosides generally result from saccharide mixtures with statistically distributed sugar residues. With multiple Saccharide attachment to an alcoholic hydroxide group result Polyglycosides of the alcohol mixtures according to the invention.
  • Polyglycosidation can be done in succession or several saccharides be used as a mixture so that the resulting functionalized Alcohol mixtures the saccharides in the form of blocks or included statistically distributed. It can vary depending Reaction conditions, in particular reaction temperature, furanose or pyranose structures result.
  • the functionalized alcohol mixtures obtained by glycosidation show a very good surface activity and can be used as nonionic surfactants in a variety of applications can be used advantageously.
  • the sulfation or phosphation of the alcohol mixtures described above or alkoxylated alcohol mixtures is carried out by Reaction with sulfuric acid or sulfuric acid derivatives to acidic Alkyl sulfates or alkyl ether sulfates or by reaction with Phosphoric acid or or phosphoric acid derivatives to acidic alkyl phosphates or alkyl ether phosphates.
  • Suitable processes for the sulfation of alcohols are the usual known to those skilled in the art, such as. B. in US 3,462,525, US 3,420,875 or US 3,524,864 are described, whereupon in full reference is made. Suitable sulfation processes are also in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. A25 (1994), pp. 779-783 and the ones cited there Literature described.
  • Is used for the sulfation of the alcohol mixtures according to the invention it is preferably 75 to 100% by weight, in particular 85 to 98% by weight.
  • Such sulfuric acid is among the Concentrations of concentrated sulfuric acid and monohydrate available.
  • a solution for sulfation with sulfuric acid or diluents can be used.
  • Suitable solvents are z. B. those that form an azeotrope with water, such as B. toluene.
  • sulfated Alcohol mixtures become the alcohol mixture in a reaction vessel submitted and the sulfating agent with constant mixing added.
  • the molar ratio from alkanol to sulfating agent preferably about 1: 1 to 1: 1.5, especially 1: 1 to 1: 1.2.
  • the sulfating agent can also be used in a molar deficit, z. B. in the sulfation of alkoxylated alcohol mixtures if Mixtures of non-ionic and anionic surfactants Connections are to be made.
  • the sulfation takes place preferably at a temperature in the range of ambient temperature up to 80 ° C, especially 40 to 75 ° C.
  • Suitable sulfating agents are e.g. B. sulfur trioxide, Sulfur trioxide complexes, solutions of sulfur trioxide in sulfuric acid (Oleum), chlorosulfonic acid, sulfuryl chloride, amidosulfonic acid etc.
  • sulfur trioxide as a sulfating agent can the implementation advantageously in a falling film evaporator, preferably carried out in countercurrent. The implementation done discontinuously or continuously.
  • the phosphating of the alcohol mixtures described above and alkoxylated alcohol mixtures are generally analog Way to sulfation.
  • Suitable processes for phosphating alcohols are the usual known to those skilled in the art, such as. B. in Synthesis 1985, Pp. 449-488 are described, to which reference is made in full here is taken.
  • Suitable phosphating agents are e.g. As phosphoric acid, polyphosphoric acid, phosphorus pentoxide, POCl 3 etc. When using POCl 3 , the remaining acid chloride functions are hydrolyzed after the esterification.
  • Another object of the invention is the use of functionalized alcohol mixtures as surfactants, dispersants, Paper auxiliaries, dirt solvents, corrosion inhibitors, Auxiliaries for dispersions, incrustation inhibitors.
  • the composition in% by weight of the active components was: 50% by weight of NiO, 12.5% by weight of TiO 2 , 33.5% by weight of SiO 2 , 4% by weight of Al 2 O 3 .
  • the throughput was 0.75 kg of raffinate II / (1 cat xh).
  • the work was carried out without recycling C 4 hydrocarbons.
  • the selectivity in% by weight was as follows: C 8 : 76.9; C 12 : 18.4 and C 16+ : 4.7.
  • the C 12 olefin fraction was obtained from the reaction mixture obtained by fractional distillation.
  • the reaction product was oxidatively decobtained after the addition of 10% strength by weight aqueous acetic acid by passing in air, and the organic product phase was hydrogenated for 10 hours with 50 g of Raney nickel at 125 ° C. and at a hydrogen pressure of 280 bar.
  • the tridecanol fraction was separated from the C 12 paraffins and from high boilers by fractional distillation of the reaction product.
  • the OH number of the tridecanol was 278 mg KOH / g. 1 H NMR spectroscopy determined 3.27 methyl groups / molecule, corresponding to a degree of branching of 2.27.
  • Sample preparation 3 drops of tridecanol were mixed with 1.5 ml N-methyltrimethylsilyltrifluoroacetamide reacted at 80 ° C for 60 min. The injection volume was 1 ⁇ l.
  • the surfactant obtained has a cloud point of 73 ° C., measured 1% in 10% butyl diglycol solution according to DIN 53 917.
  • the surface tension at a concentration of 1 g / l is 27.8 mN / m, measured according to DIN 53 914.
  • the surfactant obtained has a cloud point of 45.5 ° C., measured 1% in 10% butyl diglycol solution according to DIN 53 917.
  • the surface tension at a concentration of 1 g / l is 27.1 mN / m, measured according to DIN 53 914.
  • the surface tension of the alkyl phosphate obtained at a Concentration of 1 g / l is 32.3 mN / m, measured according to DIN 53 914.
  • the surface tension of the alkyl ether phosphate obtained a concentration of 1 g / l is 30.8 mN / m, measured according to DIN 53 914.

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  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Fats And Perfumes (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
EP00987265A 1999-11-18 2000-11-17 C13-alkoholgemisch und funktionalisiertes c13-alkoholgemisch Revoked EP1230200B1 (de)

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DE19955593 1999-11-18
DE19955593A DE19955593A1 (de) 1999-11-18 1999-11-18 C13-Alkoholgemisch und funktionalisiertes C13-Alkoholgemisch
PCT/EP2000/011440 WO2001036356A2 (de) 1999-11-18 2000-11-17 C13-alkoholgemisch und funktionalisiertes c13-alkoholgemisch

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WO2014160820A1 (en) 2013-03-28 2014-10-02 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2015148361A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2015148360A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2015187757A1 (en) 2014-06-06 2015-12-10 The Procter & Gamble Company Detergent composition comprising polyalkyleneimine polymers
WO2016032991A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016032992A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016032995A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Method of treating a fabric
WO2016032993A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016049388A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Fabric care compositions containing a polyetheramine
WO2023017794A1 (ja) 2021-08-10 2023-02-16 株式会社日本触媒 ポリアルキレンオキシド含有化合物

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DE10220799A1 (de) * 2002-05-10 2003-12-11 Oxeno Olefinchemie Gmbh Verfahren zur Herstellung von C13-Alkoholgemischen
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US8211949B2 (en) * 2007-09-24 2012-07-03 Dow Global Technologies Llc Functionalized long-chain olefin mixtures and uses therefor
KR101757936B1 (ko) 2008-12-16 2017-07-13 바스프 에스이 카르복실산 에스테르의 제조 방법
CA2746571C (en) 2008-12-16 2017-08-22 Basf Se Production of carboxylic acid esters by stripping with alcohol vapor
US20120220678A1 (en) 2009-11-03 2012-08-30 Christof Mehler Thermoplastic compositions having improved flowability
PL2576674T3 (pl) 2010-06-01 2015-02-27 Basf Se Sposób wytwarzania spienialnych kompozycji polimerów styrenowych
DE102011004675A1 (de) 2011-02-24 2012-08-30 Evonik Oxeno Gmbh C11 bis C13 Dialkylester der Furandicarbonsäure
US9561512B2 (en) 2011-04-13 2017-02-07 Basf Se Amine and diamine compounds and their use for inverse froth flotation of silicate from iron ore
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US10376901B2 (en) * 2014-09-18 2019-08-13 Akzo Nobel Chemicals International B.V. Use of branched alcohols and alkoxylates thereof as secondary collectors
CN107257807B (zh) 2015-02-23 2020-10-27 巴斯夫欧洲公司 加工含纤维素的生物质的方法
EP3266859A1 (en) 2016-07-05 2018-01-10 Basf Se Composition suitable as degreasing agent for removing greasy and/or oil type deposits
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JP7309718B2 (ja) 2017-12-20 2023-07-18 ビーエーエスエフ ソシエタス・ヨーロピア 繊維製品に付着した、融解温度が３０℃超のである脂肪化合物を除去するための洗濯用配合物
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CN116507710A (zh) 2020-12-04 2023-07-28 巴斯夫欧洲公司 免擦洗清洁组合物
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WO2014160820A1 (en) 2013-03-28 2014-10-02 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2014160821A1 (en) 2013-03-28 2014-10-02 The Procter & Gamble Company Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose
WO2015148361A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2015148360A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2015187757A1 (en) 2014-06-06 2015-12-10 The Procter & Gamble Company Detergent composition comprising polyalkyleneimine polymers
WO2016032991A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016032992A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016032995A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Method of treating a fabric
WO2016032993A1 (en) 2014-08-27 2016-03-03 The Procter & Gamble Company Detergent composition comprising a cationic polymer
WO2016049388A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Fabric care compositions containing a polyetheramine
WO2023017794A1 (ja) 2021-08-10 2023-02-16 株式会社日本触媒 ポリアルキレンオキシド含有化合物

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ATE261424T1 (de) 2004-03-15
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WO2001036356A2 (de) 2001-05-25
DE50005622D1 (de) 2004-04-15
EP1230200A2 (de) 2002-08-14
ES2217015T3 (es) 2004-11-01
KR20020050293A (ko) 2002-06-26
JP2003514785A (ja) 2003-04-22
KR100802781B1 (ko) 2008-02-12
CN1391542A (zh) 2003-01-15
DE19955593A1 (de) 2001-05-23
CN1176885C (zh) 2004-11-24
US6963014B1 (en) 2005-11-08

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